Delustering



and lustrous solutions and are more or less lustrous. Frequently how-Paemed Apt. 25, 1933 UNITED. STATES PATENT OFFICE HENRY A. GARDNER, OFWASHINGTON, DISTRICT OF COLUMBIA.

nnnus'mmno No Drawing. Original application filed July 1, 1929, SerialNo. 875,346. Divided and this application filed February 1, 1932. SerialNo. 590,330.

This invention relates to delustering; and it comprises a process ofproducing opalescence, or a flat finish, as the case may be, in fibers,films, varnishes, lacquers, etc.,

5 wherein an organosol of a metallic oxid is produced in an organicliquid not a solvent of such oxid, by dissolving an alcoholate of thecorresponding metal in said organic liquid and permitting hydrolysis toproduce such oxid, the metallic oxid being advanclaimed.

The present application is a division of my prior application Serial No.375,346, filed July 1, 1929. That application is mainly directed to themanufacture of delustered artificial silks.

The present a plication is primarily directed to the m 'ng of theorganosol compositions :irrespective of the subsequent processing ofsuch com ositions' or the type of articles obtained y such processing.

Most of the materials, the gums, resins,-

cellulose esters and ethers, etc., used in making films, filaments andvarnishes, when dissolved in solvents tend to 've transparent tfiiafinal products ever a silky opalescence to transmitted light or a flatfinish b reflected light is deemed more desirable. pacity and, to some'extent, flatness can be and areattained by the use of the ordinary finefillers mixed. with the composition, such as barium sulfate or titaniumdioxid; but these materials as commercially obtainable aretoo coarsegrained 0 to get the best results from an optical point of view.

It is the object of the present invention to provide a new method ofobtaining opalescence or flatness, as the case maybe, giving superiorresults. To this end, I utilize the optical properties of organosols ofmetallic oxids; producing an extremely fine dispersion of variousmetallic oxids in solvents emplo ed for making films and filaments byadd i ng to the solvent :3; hydrolyzable alcoholate of a metal, suchalcoholate being soluble in or miscible with the said solvent and thecorresponding metal oxid being insoluble in such solvent and permittinghydrolysis therein. The metal alcoholates best adapted for my purposesin giving translucence are those derived from TiO and Z10 although amultiplicity of other metallic oxids can be used, some of these beinghereinafter indicated. While it is ordinarily assumed thatneithertitanium or zirconium gives alcoholate derivatives, I have found that.these can be easily made by processes described post. These metalalcoholates dissolved in organic liquids are sensitive to moisture andcan be readily hydrolyzed to give organosols.

Speaking more specifically of titanium compounds, titanium tetrachloridcan be converted into titaniumtetraethylate by the action-of metallicsodium and ethyl alcohol, sodium ethylate being probably first formed.The sodium chlorid produced is-insoluble and. can be readily separatedfrom the liquid products of reaction. The new compound produced,titanium tetraethylate, when freed from any excess of alcohol, is athin, mobile liquid with a boiling point of 200 C. at

of moisture giving an extremely fine dispersion or organosol of TiOprobably in hydrated form, or as the so-called titanic acid. Zirconiumtetraethylate may be made by a similar method and has similar propervties. Zirconium tetraethylate may also be' distilled under vacuum. Lowerboiling but similar compounds may be made by using methyl alcohol inlieu of ethyl alcohol; and still higher boiling compounds by the use ofthe higher alcohols, propyl, butyl, pentyl, etc.

These alcoholates of titanium and zirconium are soluble in a variety-oforganic liquids, including alcohol, light petroleum dlstillates andtoluol.

Solutions of any of these alcoholate compounds in absolute alcohol,hydrocarbons,

etc., are clear, but on addition of even traces of water, hydrolysis atonce occurs with production of insoluble bodies of colloidal fineness ina dispersed condition. According to the quantity of metal alcoholatepresent, the result may vary from a simple opalescence to the formationof a stiff gel or jelly. Because of the extremely fine particle size inthese dispersions, all the sols and gels produced are translucent ratherthan opaque. For example, by adding 1 cc. of titanium tetraethylate to10 cc. of a mixture of 95 per cent alcohol and ether, a dense, stiffjelly is formed by the water present in the alcohol. The jelly ishowever quite translucent, indicating an extreme fineness of subdivisionin the TiO: formed.

The present invention may be utilized in many directions. In makingvarnishes and 4 lacquers opalescent to transmitted light and flat toreflected light, a small amount of titanium tetraethylate or one of theother alcoholate compounds mentioned may be added to one of the solventsused in making the varnish or lacquer. In making automobile lacquers,for example, opalescent or flat, an ordinary lacquer is mixed with alittle titanium tetraethylate, dissolved in alcohol or toluol.Ordinarily, there is enough moisture present in the lacquer to producethe desired organosol. The present invention is even of advantage wherethe lacquer carries incorporated pigment in amount sufiicient to make itopaque, since it destroys the luster of the surface layers of the drylacquer and gives a flat efi'ect. Similarly, titanium tetraethylate, orone of the other compounds mentioned, may be dissolved in an anhydroussolvent and added to the compositions used in making celluloid articles,nitrocellulose threads (Chardonnet silk), acetylcellulose threads, etc.

I regard the present invention as particularly useful with artificialsilk made from either nitrocellulose or acetylcellulose,

since it enables the production of a silky opalescence, obviating thehigh luster of the ordinary threads. An additional advantage is thegreater ease of dyeing of the delustered threads, since titaniumhydroxid and zirconium hydroxid are excellent mordants; their presenceenabling the use of a wide variety of dyes not otherwise applicable tothese artificial silks.

The color of the dispersed particles of TiO or Z10 is white and theygive a pearly or silky opalescence; but the particles may be" dyed anycolor, giving a correspondingly tinted opalescence. This may be done bydissolving a basic dye in the alkylate solution. On hydrolysis, thehydroxid particles take up or adsorb the dye.

. In a specific embodiment of the present invention, employing titaniumtetraethylate to make delustered silk with a silky opal.-

escence, 1 part by volume of liquid titanium tetraethylate was dissolvedin 10 parts of absolute alcohol. The solution was mixed with 100 partsof a mixture of ethyl ether and alcohol in the proportion of 60:40, thealcohol being ordinary- 95 per cent. A white but translucent jellyformed. Nitrocellulose in the proportion of 25 per cent by weight wasadded and the mixture stirred until a good solution was obtained. Thetranslucent preparation obtained was forced through capillaries to formthreads in the usual method adopted to form artificial silk; the fiberbeing subsequently denitrated and otherwise processed as usual. Thefinal delustered silk had a translucent, dull appearance like that ofnatural silk. While I added the titanium tetraethylate to thealcohol-ether before dissolving the nitrocellulose, the nitrocellulosecan be as well first dissolved and then the tetraethylate added.

Cellulose acetate silk of dull translucent appearance may be formed in asimilar manher. In one particular case, I dissolved about 20 per cent ofcellulose acetate in acetone and added up to 10 per cent of an absolutealcohol solution of zirconium tetraethylate. This gave a highlycolloidal dispersion of ZrO or its hydrate. The translucent solution wasused, as before, for making fibers by extrusion.

Cellulose acetate silk and nitrocellulose silk formed in the manner justdescribed both have the silky translucency of natural silk and thegeneral appearance of natural silk. Unique silks may be made by adding asmall proportion of a basic dye to the solution of titanium or zirconiumtetraethylate. On hydrolysis, the very finely dispersed particles ofhydroxid are tinted and the resulting silk has a peculiar tintedopalescence. By the use of a very small amount of a blue dye, abrilliant white opalescence is obtained, this amount of blue dye servingto compensate for the natural yellow of the fiber.

While I have spoken more specifically of titanium and zirconiumcompounds and while I regard them best adapted for my'purposes, a widevariety of other metals forming alcoholate derivatives hydrolyzed bywater may be used in their lieu. Aluminum, magnesium and zinc compoundsmay be mentioned. For special purposes, metals having colored oxids,suchas cobalt and nickel, may be used. While cobalt and nickel are notpresumed to form direct connected alkyl derivatives, their chlorids,bromids and iodids in alcoholic solution will give di-alcoholatederivatives on treatment with sodium. All of these metals, like titaniumand zirconium, give oxids which are normally insoluble in all neutralorganic solvents while they form'alcoholate compounds which are solublein these solvents and can be hydro lyzed by minimal amounts of water togive oxids or hydrated oxids insoluble in the organic solvent and inwater.

Linseed oil may be used asa dispersion medium by incorporating thereinhydrolyzable" alkylated compounds of cobalt, manganese, vanadium orlead. Hydrolysis of these compounds causes the formation of organosolsof the corresponding metal o'xids. The so-treated linseed oil is quickdrying owing to the catalytic elfect of the metal oxids and gives adesirable flat finish. It

may be added to compositions for forming films, that is, coatingcompositions.

What I claim is: g

1. In the delustering and flatting of films, filaments, sheets andlayers produced from liquid compositions, the procss which comrisesadding to the liquid composition a hydrolyzable alcoholate of a metal,said metal being selected from the class consisting of titanium,zirconium, aluminum, magnesium, zinc, cobalt and nickel and'eflecting hydrolysis of said alcoholate to obtain said delustering and flattening.

2. In the delustering or flatting of var-;

nishes, lacquers, artificial silks, filaments and sheets produced fromliquid material, the process which comprises adding to the material asolution of hydrolyzable alcoholate of zirconium.

3. In the delustering of varnishes, lacingvarnishes and the likeproduced from liquid material, the steps which comprise adding tolinseed oil, an alcoholate of a metal, said metal being selected fromthe class consisting of titanium, zirconium, aluminum, magnesium, zinc,cobalt' and nickel, and hydrolyzing in situ the saidalcoholate.

8. In the manufacture of delustered and flattened films, filaments,sheets, layers and the like from liquid compositions containing anorganic liquid component, the imquers, artificial silks, filaments andsheets produced from liquid material containing a cellulose compound,the process which comprises adding to the liquid material a solution ofa hydrolyzable alcoholate of a metal, said metal being selected from aclass con sisting of titanium, zirconium,- aluminum,

magnesium, zinc, cobalt and nickel 4. In the delustering of varnishes,lacquers, artificial silks, filaments and sheets prises adding to theliquid material a soluproduced from liquid material-containing acellulose compound, the process which comtion ofa hydrolyzablealcoholate of zirconium.

' 5. In processes of making delustered, colored materials, the stepswhich comprise adi so mixing a dye with a solution ofan alcoholate of ametal, said metal being selected from a class consisting of titanium,zirconium, aluminum, magnesiimi, zinc, cobalt and v nickel andhydrolyzing the said alcoholate in situ, thus dyeing the metalliccompounds, produced by said hydrolysis, with said dye.

6. In processes of delustering and flattening varnishes and the likeproduced from liquid materials, the process which comprises adding tothe liquid material, a solution of a hydrolyzable alcoholate of a metal,said metal being selected from a class consisting of titanium,zirconium, aluminum, magnesium, zinc, cobalt and nickel, andhydrolyzing, in situ, the said alcoholate.

7 Inprocesses of delustering and flatten--

